Hydrophobic expanded graphite-covered support to construct flexible and stable SERS substrate for sensitive determination by paste-sampling from irregular surfaces.

Surface enhanced Raman spectroscopy (SERS) is a promising technique for trace determination. More and more attention is focused on hybrid SERS substrates, which coupled with noble metal nanoparticles and carbon-based materials. Herein, expanded graphite (EG) is used to prepare EG-covered support by ultrasonic washing and filtration. Such support is flexible and can be cut into any shape. And the contact angle (θe) for Au nanorods (Au NRs) sol on the EG-covered support was 108.2° and the hydrophobic surface is helpful for Au NRs to construct 'hot spots' during evaporation. The limits of detection (LOD) for crystal violet (CV), thiram, malachite green (MG) and methylene blue (MB) were as low as 1 ppb, 50 ppb, 1 ppb and 1 ppb, respectively. Moreover, a fast and convenient 'paste-sampling' method could be employed for trace contaminants on real samples, because EG-based Au NRs substrate is of flexibility and porosity. Thus, CV residue on shrimp could be determined lower than 1 ppb and thiram residue on grapes could be identified lower than 50 ppb. In addition to high sensitivity, the stability of EG-based Au NRs substrate is also very good. Even after acid/alkali pretreatment (pH = 4∼10) or 30 min of thermal treatment (T = 20∼100 °C), the enhancement of the substrate remained stable. What's more, the substrate could be stored as long as 30 days. The highly stable, sensitive, cost-effective and easy-to-produce EG-based Au NRs substrates exhibit a great potential to promote application of SERS for routine analysis.